The traditional strategies for the synthesis of 1,5-benzodiazepines basically rely on the condensation reactions of o-phenylenediamines with α,β-unsaturated carbonyl compounds,(5) β-haloketones,(6) or ketones(5a, 7) (Scheme 1, paths a–c). These reactions can offer effective methods for the synthesis of 1,5-benzodiazepines. However, they inevitably suffer from unsatisfactory atom economy. Therefore, from the sustainable and atom-economic synthesis point of ...